Method for improving clay brightness utilizing magnetic separation

ABSTRACT

A method for brightening a kaolin clay wherein an aqueous dispersion is initially formed of said clay, which dispersion is blunged and conditioned and the resultant slurry thereupon subjected to a froth flotation treatment to remove titaniferous impurities. The purified product from the froth flotation treatment is thereupon subjected to magnetic separation by passing such product through a slurry-pervious ferromagnetic matrix positioned in a high intensity magnetic field, which results in substantial, additional brightening of the clay.

BACKGROUND OF THE INVENTION

This application is a continuation-in-part of my co-pending application,Ser. No. 513,154, now U.S. Pat. No. 3,974,067 filed Oct. 8, 1974, andentitled "METHOD FOR IMPROVING CLAY BRIGHTNESS UTILIZING MAGNETICSEPARATION".

This invention relates generally to methods for beneficiation of kaolinand other clays, and more specifically relates to a method for improvingthe brightness of kaolin clays or the like through the conjunctive useof a high intensity magnetic field.

Natural clays, including kaolin clays, frequently include discoloringcontaminants in the form of iron and/or titanium-based impurities. Thequantities of titanium-based impurities are particularly significant inthe case of the sedimentary kaolins of Georgia, where such impuritiesare commonly present as iron-stained anatase and rutile. In order,therefore, to refine the clay and bring the brightness characteristicsof the resultant product to a level acceptable for paper coatingapplications, various techniques have been used in the past to removesuch discoloring impurities. Thus, for example, hydrosulfites have beenwidely used for converting at least part of the iron-based (or"ferruginous") impurities to soluble forms, which may then be removedfrom the clay.

Among the most effective methods for removing titaniferous impurities,including e.g. iron-stained anatase, are the well-known froth flotationtechniques. According to such methods an aqueous suspension or slurry ofthe clay is formed, the pH of the slurry is raised to an alkaline value,for example, by the addition of ammonium hydroxide, and a collectingagent is added, for example, oleic acid or a similar fatty acidcollecting agent. The slurry is then conditioned, by agitating same fora relatively sustained period. A frothing agent, for example, pine oil,is added to the conditioned slurry, after which air is passed throughthe slurry in a froth flotation cell, to effect separation of theimpurities.

Within recent years it has been contemplated that magnetic separationtechniques might be utilized in order to remove certain of theaforementioned impurities, including titaniferous impurities as well ascertain ferruginous matter. Anatase, for example, and certain otherparamagnetic minerals have been found to respond to high intensitymagnetic fields. Thus in U.S. Pat. No. 3,676,337 to Henry H. Kolm, forexample, a process is disclosed for treating slurries or the like bypassing same through a steel wool matrix in the presence of a backgroundfield of at least 12,000 gauss. Such process has been found useful inremoving the aforementioned contaminants from kaolin slurries. Theapparatus disclosed in Marston, U.S. Pat. No. 3,627,678, is similarlyutilizable in separating the aforementioned impurities from a clayslurry. In this latter instance, the slurry to be treated is thus passedthrough a canister including a stainless steel or similar filamentarymatrix, while a high intensity magnetic field is impressed on the saidmatrix.

A study of the prior art including the patents cited, will demonstratethat prior researchers have considered flotation technology on the onehand and magnetic separation treatment on the other, to be alternateapproaches to the impurity-removal problem. The explanation of thisappears to be that froth flotation has been considered so effective inremoving titaniferous impurities, that it has been believed that nosignificant advantage could derive from subsequent use of magneticseparation --except for removal of ferruginous matter, which in anyevent is removable by normal leaching.

SUMMARY OF INVENTION

Now in accordance with the present invention, it has been unexpectedlyfound, that clay slurries after being subjected to a thorough frothflotation treatment, may yet be substantially improved in leachedbrightness characteristics, by subjecting the purified slurry to furthertreatment in a high intensity magnetic field. It has been found as oneaspect of the present discovery, that where the slurry product offlotation is analyzed prior and subsequent to magnetic treatment, thechanges in TiO₂ and Fe₂ O₃ content is so small as to not fully explainthe observed brightness improvement. It is therefore hypothesized thatthe froth flotation process, in some manner not fully understood, inaddition to removing titaniferous impurities, renders other contaminantsin a form enabling these contaminants to thereupon respond to the highintensity magnetic field. Such a result may, for example, be broughtabout by the relatively high amounts of energy dissipated during theconditioning process incident to froth flotation; or may be broughtabout by the combination of energy dissipation with the chemical agentsutilized in flotation, such as the fatty acid collector agents, etc.; orby other aspects of the froth flotation process. In any event, and inconsequence of such treatment, it appears that certain heretoforeunresponsive impurities, possibly including mica for example, may thenbe effectively removed by the magnetic techniques previously mentioned.

The magnetic separation step of the present invention is preferablybrought about by passing the aqueous clay slurry through aslurry-pervious ferromagnetic matrix, while a high intensity magneticfield is applied at the matrix. The said field may be generated byelectromagnets or other field sources, which at least partially surrounda non-magnetic canister in which the matrix is packed. The matrixmaterial, as is known in the art, preferably comprises a packedstainless steel wool; although other filamentary or strand-likematerials may be effectively used for this purpose; as may matrices ofsteel balls, tacks, and of other slurry-pervious ferromagneticmaterials.

The average field intensity maintained at the matrix during theseparation process is in the general range of 7 to 22 kilogauss; and apreferable field intensity during the separation process is about 15 to20 kilogauss. The slurry is passed through the matrix at such a rate asto be maintained in the field for at least 15 seconds, with from 1/2 to2 minutes retention time being preferred. Subject to the effect onprocessing rates, longer retention times are also acceptable; and canoccur from either a single pass or via cumulative passes through thematrix. The slurry as passed to the magnetic separator typicallyincludes from about 15 to 45% solids, with 15 to 35% solids beingpreferable.

DESCRIPTION OF PREFERRED EMBODIMENT

In accordance with the present invention, the kaolin or other clay to bebrightened, is initially processed through a series of steps whichincludes subjecting such clay to a froth flotation treatment. In apreferable procedure, for example, the crude clay is blunged andconditioned by forming an aqueous, alkaline, dispersion of the clay (pHadjusted to about 7 to 10 with ammonium hydroxide), which dispersion mayinclude as a deflocculating agent a water soluble salt of a polyacrylicacid or a polymethacrylic acid, preferably having an average molecularweight in the range of 500 to 10,000; together with sodium silicate; andoleic acid or other fatty acid collector agent. Where employed, thepolyacrylate and/or polymethacrylic salts are typically present fromabout 1/2 to 3 lbs/ton; suitable materials of this type are, forexample, available from Allied Colloids, Great Britain, under the tradename "Dispex" (e.g. "Dispex N-40). Sodium silicate is present in a rangefrom about 1/2 to 16 lbs/ton; and the fatty acid collector agent such asoleic or linoleic acid etc. up to about 12 lbs/ton; preferably in therange of about 2 to 4 lbs/ton. The blunging and conditioning steps arepreferably conducted simultaneously, whereby the oleic acid, linoleicacid, or similar fatty acid collector agent may partially function as adispersant, thereby enabling minimization of the quantity of sodiumsilicate used--which has been found to be advantageous in that sodiumsilicate when present in excess acts as a depressant during frothflotation.

The slurry during the aforementioned blunging and conditioningoperations may include from about 20 to 70% solids, but preferablyincludes a relatively high solids content, i.e. from about 35 to 60%solids. The conditioning process is preferably continued for asufficient time to dissipate at least 25 hp-hrs of energy per ton ofsolids, although more generally the invention is effective where aslittle as 10 hp-hrs per ton of solids of energy is dissipated. Theblunged and conditioned slurry, after addition of a frothing agent as,for example, pine oil, is then subjected to a conventional treatment ina froth flotation cell, i.e. air is passed through the slurry in saidcell to effect separation of impurities from the clay.

With the exception of the preferred use in the present invention ofsimultaneous blunging and conditioning as heretofore mentioned, themethods thus far described comprise, per se, conventional frothflotation techniques for purifying kaolin clays, particularly oftitaniferous impurities; and in this connection further details of frothflotation treatment are set forth at numerous patents of the prior artas, for example, in U.S. Pats. No. 2,990,958; 3,138,550 and 3,450,257.

As has heretofore been mentioned, it has previously been assumed thatthe froth flotation technology was as effective or more effective thanmagnetic separation in removing titaniferous impurities. It seemedfurther that no advantage could flow from subsequent use of a magneticseparation step, in that the ferruginous impurities which presumablymight thereupon be removed, could in any event be removed byconventional leaching. In accordance with the present invention,however, it has unexpectedly been discovered that the froth flotationprocess as herein practiced can, on the contrary, serve as a prelude toa magnetic separation treatment which thereupon effects highlysignificant and unexpected improvements in the already substantiallyrefined clay. In order to demonstrate the efficacy of this conjunctivetreatment, a series of Examples are now set forth, wherein crude Georgiakaolins are subjected to froth flotation treatment in accordance withthe prior discussion, and are then processed by conventional leach anddewatering treatments to establish leached brightness levels for theensuing samples. Comparative results are then set forth wherein thesamples emerging from the froth flotation process are subjected tomagnetic separation; and then to comparable leaching and dewateringtreatments to yield comparison brightness values.

EXAMPLE I

In this Example a representative sedimentary soft Georgia kaolin wassubjected to the aforementioned sequence of treatments culminating intreatment in a froth flotation cell. The said treatments were allconducted in an industrial plant environment, and the total amount ofenergy dissipated during blunging and conditioning was at least 25hp-hr/ton of solids. The purified product, as derived from the flotationcell, was found (unleached) to display a G.E. brightness of 87.5. In allinstances in this specification it will be understood that brightnessvalues are obtained according to the standard specification establishedby TAPPI procedure T-646m-54. Comparable leached brightness values wereobtained by centrifuging the said plant flotation product to yield asubstantially minus 3-micron fraction, and subjecting same to aconventional leaching treatment with sodium hydrosulfite at an additionlevel of 8 lbs/ton. The resultant leached brightness was 90.7. The TiO₂content before leaching, was measured at 0.38%, and the Fe₂ O₃ content,at 0.42%.

For further purposes of comparison, crude clay samples were divertedfrom the feed to the blunger, i.e. at the aforementioned plant, andsubjected to the same schedule of blunging, conditioning and frothflotation -- this time, however, in a laboratory environment wherein theparameters of treatment are more precisely regulatable. During suchtreatment ammonium hydroxide (calculated at 100% ammonia) was typicallyadded at about 3.9 lb/ton of dry clay; oleic acid in concentration ofabout 3.7 lb/ton; and sodium silicate in concentration of about 2.7lb/ton. The total dissipated mechanical work during the process, farexceeded 25 hp-hr/ton of solids. The unleached brightness of a samplefrom the flotation treatment was found to be 88.5 in this instance; andthe leached brightness of the laboratory-floated clay (again utilizing 8lbs/ton of hydrosulfite) was found to be 90.8. The TiO₂ content in thisinstance was 0.22% and Fe₂ O₃ content 0.48%. Since a mathematicalanalysis of the chemical analysis techniques utilized, indicates aprobable error in TiO₂ analysis of ± 0.07%, the comparison betweenlaboratory and plant flotation indicates that the plant flotationmethodology is indeed performing its function and very effectivelyremoving the titaniferous impurities.

Samples emerging from the plant flotation cell (brightness level of87.5) were then subjected to treatment in a high intensity magneticfield. The slurry samples thus treated included 30% solids content(after being diluted, as appropriate), were passed through the magneticseparator at a pH of about 9.3, and at a temperature of approximately30° C. The apparatus utilized was of the general type illustrated in theaforementioned Marston U.S. Pat. No. 3,627,678, and thus generallycomprised a canister packed with a stainless steel wool at whichenveloping magnets provided an approximate field intensity of about 15.5kilogauss during the separation process. The stainless steel wool had a7.5% packing, by which it is meant that 7.5% of the canister volume waseffectively occupied by the matrix material. During the magnetictreatment the flow rate of the slurry was such that retention time inthe magnetic field was approximately 1.2 minutes. The samples emergingfrom the magnetic separator were thereupon flocculated at a pH of 3,after which a conventional leaching step was effected by addition ofsodium hydrosulfite, followed by conventional dewatering etc. to yield atest sample. The results of the foregoing operations are set forth inTable I hereinbelow:

                  Table 1                                                         ______________________________________                                                          #/ton                                                       Feed Time                                                                             Product   Leached Brightness                                                                            TiO.sub.2                                                                          Fe.sub.2 O.sub.3                       Mins.   Brightness                                                                              2      4    6    8    %    %                                ______________________________________                                         4.5    89.8      91.5   91.5 91.7 91.4 0.34 0.38                              9.0    89.4      90.2   91.3 91.1 91.1 0.42 0.48                             18.0    89.0      90.2   90.8 91.2 91.4 0.38 0.36                             27.9    89.2      91.1   91.3 91.3 91.3 0.34 0.37                             5 passes of                                                                           88.7      91.3   91.4 91.4 91.5 0.26 0.38                             27 mins.                                                                      ______________________________________                                    

The brightnesses specified in Table I are all obtained in accordancewith the procedures heretofore described. The first four tabularizedfeed time values indicate that after operating the separator for thetime specified, a sample of the total volume emerging from the magneticseparator (after one pass) was subjected to brightness testing. Forexample, in the first instance, after a period of 4.5 minutes of runningtime, a sample of the total product from the separator was taken as itemerged from the separator and found to have an unleached productbrightness of 89.8. These same samples were similarly found to haveleached brightnesses, with various addition levels of sodiumhydrosulfite, as is indicated under the addition levels of 2, 4, 6 and 8pounds per ton of the leach agent. After 41/2 minute operation themagnetic separator matrix was flushed, and a second run initiated, whichthen was continued for 9 minutes, after which samples were again takento yield the data proceeding to the right of the Table. The generaldecline in brightness levels with increasing running time is, of course,due to growing contamination of the separator matrix.

Finally, there is tabulated as the last entry in Table I, an instancewhere the slurry was passed successively five times through the matrix,the operating time for effecting each pass of the entire sample being 27minutes.

It will be noted from Table I that very substantial improvements in thebrightnesses of the samples were obtained both with and withoutadditional leaching. An equally significant finding is apparent from theTiO₂ and the Fe₂ O₃ contents, which are tabularized at the right-handside of the Table. (The TiO₂ and Fe₂ O₃ contents set forth in Tables 1through X of this specification, are all derived from analyses of theunleached samples.) When these values are compared with the TiO₂ and Fe₂O₃ values previously given for samples which had been floated but notsubjected to magnetic separation (see above); and further when accountis taken of the cited measuring error of about ± 0.07% in TiO₂determination; it becomes evident that the bulk of staining TiO₂ has infact been removed by the prior flotation process; and that very littlefurther effect has been had upon either the TiO₂ or Fe₂ O₃ content as aresult of the magnetic separation. These facts, when taken in comparisonto the very marked improvement in brightness level, strongly suggestthat the staining impurities removed during magnetic separation, areother than the two factors tabularized. Possibly, for example, aspreviously suggested, the element being acted upon is mica, although itis possible that additional staining elements as yet unknown, havingbeen rendered tractable by the prior conditioning and froth flotationprocess, are removed by the magnetic separation.

EXAMPLE II

In this Example the clay sample taken from the plant after frothflotation exhibited a brightness of 87.1; and a minus 3-micron fractionobtained therefrom by centrifuging was found after leaching (utilizing aleach additional level of 8 lbs. sodium hydrosulfite per ton) to exhibita brightness of 89.6. The TiO₂ content of the unleached sample was 1.01,and the Fe₂ O₃ content 0.72. A comparable sample taken from the feed tothe blunging and conditioning apparatus, and froth flotation processedunder laboratory conditions, exhibited a product brightness of 87.1. Thelaboratory-floated sample further, exhibited leached brightnesses of89.5 at 2 lbs./ton hydros (sodium hydrosulfite) addition; 90.1 at 4lbs./ton hydros addition; 90.3 at 6 lbs./ton hydros addition, and 90.6at 8 lbs./ton hydros addition. The TiO₂ content of thelaboratory-floated sample was 0.40%, and the Fe₂ O₃ content was 0.70%.

Utilizing the same magnet condition as described in connection withExample I, and with an input slurry solids content of 30%, and pH of9.5, the brightness improvements indicated in Table II below wereobtained, where in each instance the parameters identified are inaccordance with the discussion had in connection with Example I. It willagain be noted here that a very substantial increase in productbrightness has been obtained -- particularly in comparison to the plantproduct brightnesses, but also in comparison to the laboratory processedsamples. Such improvement is particularly evident at reduced levels ofleach addition. Again it will be noted that the differences in TiO₂ andFe₂ O₃ content in comparison to the contents of these contaminants wherefroth flotation alone is practiced, is relatively small --where thelimits of experimental error are taken into account.

                  Table II                                                        ______________________________________                                                          #/ton of hydros                                             Feed Time                                                                             Product   Leached Brightness                                                                            TiO.sub.2                                                                          Fe.sub.2 O.sub.3                       Mins.   Brightness                                                                              2      4    6    8    %    %                                ______________________________________                                        4.5     89.7      91.1   91.2 91.2 91.2 0.50 1.0                              9.0     89.9      90.5   91.5 91.5 91.5 0.48 1.1                              18.0    89.7      90.3   90.8 91.1 91.2 0.45 0.99                             27.0    89.7      90.6   91.1 91.1 91.1 0.49 0.98                             ______________________________________                                    

EXAMPLE III

In this instance a further formulation of a soft sedimentary Georgiakaolin clay crude was utilized. A sample here, taken directly from theoutput of the flotation plant, exhibited a product brightness of 86.9;and a minus 3-micron fraction derived therefrom, and treated at a leachadditional level of 8 lbs./ton, displayed a 90.5 brightness. TiO₂content of the unleached sample was 0.50%, and Fe₂ O₃ content was 0.50%.

Again in this Example the comparable laboratory-processed sample (minus3-micron fraction) exhibited a product brightness, without leachaddition, of 88.2; and where 8 lbs./ton of hydros were utilized,exhibited a leached brightness of 91.7. TiO₂ content of the unleachedlaboratory-processed sample was 0.30%, and Fe₂ 0₃ content was 0.67%.

Samples from the output of the flotation plant were processed as in theforegoing Examples, at a solids content of 30%. and a pH of 9.5. Data asset forth in the following Table III was obtained under such conditions,where the identification for such data is in accordance with priordiscussion. Once again it is noted that very significant improvement inthe product brightnesses are obtained in comparison to either the plantprocesses or those yielded where samples are froth flotation-processedunder laboratory conditions. These brightness improvements again, areparticularly significant at low levels of leach addition, or where leachis not used at all; and once again it is noted that the TiO₂ and the Fe₂O₃ content, within the limit of experimental error, are notsignificantly altered by treatment in the magnetic field, therebysuggesting that the observed improvements are in response to removal ofother contaminants than these two fractions.

                  Table III                                                       ______________________________________                                                          #/ton of hydros                                             Feed Time                                                                             Product   Leached Brightness                                                                            TiO.sub.2                                                                          Fe.sub.2 O.sub.3                       Mins.   Brightness                                                                              2      4    6    8    %    %                                ______________________________________                                         4.5    89.4      91.0   91.3 91.4 91.4 0.36 0.41                              9.0    89.0      90.0   91.1 91.3 91.3 0.34 0.46                             18.0    88.3      90.2   90.4 90.5 90.5 0.42 0.48                             27.0    88.6      90.4   90.9 91.1 90.8 0.50 0.43                             5 passes of                                                                           90.2      91.3   91.7 91.7 91.6 0.32 0.35                             27 mins.                                                                      ______________________________________                                    

In Examples IV through VIII; now to be set forth, the practicaldifficulties attendant on performing tests of the present inventionunder full-scale industrial conditions, were eliminated by conductingall tests under laboratory conditions. In particular, a first set ofsamples of soft sedimentary Georgia kaolins were subjected to blunging,followed by a magnetic separation step. A second set of similar sampleswere subjected to a laboratory flotation by thoroughly blunging andconditioning the samples with about 3.7 lb/ton ammonium hydroxide,(calculated as 100% ammonia) oleic acid in concentration of about 3.7lb/ton and with about 2.7 lb/ton of sodium silicate. Total mechanicalwork dissipated during blunging and conditioning, considerably exceeded25 hp-hrs./ton of solids. Finally, a third set of the samples weresubjected to the flotation treatment mentioned, and thereupon passedthrough the magnetic separator. In each instance magnetic separation waseffected in a steel wool matrix and at an average field intensity ofapproximately 15.5 kilogauss; and the slurry was passed through theseparator at a dilution of about 15-30% solids, with the pH beingadjusted to approximately 9.5 by ammonium hydroxide. In each instance inthe Tables of the Examples, brightnesses are determined in accordancewith the procedure previously identified, and for various levels ofleach addition, ranging from 0 to 8 lbs/ton of sodium hydrosulfite.

EXAMPLE IV

In this Example the crude clay samples utilized had measuredbrightnesses of 83.5; TiO₂ content of 1.30%; and Fe₂ O₃ content of0.20%. The brightness data obtained, in accordance with the discussionof the proceeding paragraph is set forth in Table IV below:

                  Table IV                                                        ______________________________________                                                      Hydros addition                                                          Pro- per ton         TiO.sub.2                                                                            Fe.sub.2 O.sub.3                         Test       duct   2#     4#   6#   8#   %    %                                ______________________________________                                        Blunge & one pass                                                                        86.9   88.4   88.9 88.9 89.0 0.65 0.15                             through Mag. Sep.                                                             Lab-Floated alone                                                                        85.1   86.7   88.5 88.5 88.7 0.65 0.25                             Lab-Floated & one                                                             pass through Mag.                                                             Sep.       90.0   90.7   90.9 90.9 90.8 0.70 0.23                             ______________________________________                                    

EXAMPLE V

The clay samples used here exhibited a crude brightness of 84.6. TheTiO₂ content of the crude was evaluated at 1.47%, and the Fe₂ 0₃ contentas 0.23%. Data was obtained for these samples as set forth below inTable V.

                  Table V                                                         ______________________________________                                                      Hydros addition                                                          Pro- per ton         TiO.sub.2                                                                            Fe.sub.2 O.sub.3                         Test       duct   2#     4#   6#   8#   %    %                                ______________________________________                                        Blunge & one pass                                                                        87.3   90.8   90.5 90.5 90.5 0.92 0.17                             through Mag.Sep.                                                              Lab-Floated alone                                                                        87.8   90.4   91.2 91.4 91.4 0.65 0.17                             Lab-Floated & one                                                             pass through Mag.                                                             Sep.       89.5   91.0   92.1 92.3 91.9 0.52 0.09                             ______________________________________                                    

EXAMPLE VI

In this instance the crude clay samples displayed brightnesses of 82.2;the TiO₂ content was 1.34%; and the Fe₂ O₃ content, 1.09%. The datayielded upon testing of these crudes in accordance with the foregoingprocedures is set forth in Table VI below.

                  Table VI                                                        ______________________________________                                                      Hydros addition                                                          Pro- per ton         TiO.sub.2                                                                            Fe.sub.2 O.sub.3                         Test       duct   2#     4#   6#   8#   %    %                                ______________________________________                                        Blunge & one pass                                                                        84.7   87.2   89.1 89.1 89.1 0.90 0.97                             through Mag.Sep.                                                              Lab-Floated alone                                                                        86.8   88.9   89.8 90.4 91.5 0.16 1.08                             Lab-Floated & one                                                             pass through Mag.                                                             Sep.       91.3   92.5   92.5 92.5 92.6 0.10 0.82                             ______________________________________                                    

EXAMPLE VII

The yet further group of samples utilized in this test, had a crudebrightness of 79.9; a TiO₂ content of 1.47%; and an Fe₂ O₃ content of0.40%. The associated data yielded upon testing of these samples is setforth in Table VII below.

                  Table VII                                                       ______________________________________                                                      Hydros addition                                                          Pro- per ton                                                         Test       duct   2#     4#   6#   8#   %    %                                ______________________________________                                        Blunge & one pass                                                                        83.1   85.3   88.0 88.1 88.2 0.89 0.35                             through Mag. Sep.                                                             Lab-Floated alone                                                                        83.0   83.7   85.6 86.8 88.8 0.37 0.38                             Lab-Floated & one                                                             pass through Mag.                                                             Sep.       88.1   8.9    89.8 90.3 91.3 0.37 0.30                             ______________________________________                                    

EXAMPLE VIII

In this instance the samples utilized displayed a brightness from thecrude of 82.1. The TiO₂ content was 1.27%; and the Fe₂ O₃ content 1.18%.The pertinent data yielded upon testing these samples in accordance withthe prior procedures, appears below as Table VIII.

                  Table VIII                                                      ______________________________________                                                      Hydros addition                                                          Pro- per ton         TiO.sub.2                                                                            Fe.sub.2 O.sub.3                         Test       duct   2#     4#   6#   8#   %    %                                ______________________________________                                        Blunge & one pass                                                                        85.1   87.0   87.1 87.1 87.1 0.81 1.06                             through Mag.Sep.                                                              Lab-Floated alone                                                                        86.0   88.3   89.4 89.9 90.4 0.30 1.13                             Lab-Floated & one                                                             pass through Mag                                                              Sep.       89.4   90.5   90.5 90.5 90.5 0.30 0.78                             ______________________________________                                    

EXAMPLE IX

In this instance the process of the present invention was practiced,utilizing as the clay samples the "Alphaplate" product of the assigneecorporation. The designated product is a relatively coarse particle sizedelaminated Georgia kaolin clay. The samples utilized in the tests wereplant-derived, and taken after the delamination operation, but prior toleaching. Said samples, in accordance with the usual mode of productionof the "Alphaplate" product had already been subjected to a conventionalfroth flotation process, i.e. prior to delamination. The solids contentof the slurry into the magnetic separator was, in this instance, 40%,and the pH was 8.0. The flow rate was such as to permit a residence timein the magnetic separator of approximately 1.2 minutes with the averagefield intensity being approximately 15 kilogauss. Table IX below, setsforth comparative brightness yielded for three sets of runs, where ineach instance comparative data appears with and without the use of themagnetic separation step. The advantages yielded by the said subsequentstep, are evident. It may once again be observed that though reductionin TiO₂ content does result from the magnetic separation, in general thechange in TiO₂ and Fe₂ O₃ in consequence of magnetic separation (ascompared to the TiO₂ and Fe₂ O₃ in samples which have been leached, butnot subjected to magnetic separation) is so small as to not account forthe relatively large increases in brightness.

                  Table IX                                                        ______________________________________                                                      Hydros addition                                                          Pro- per ton         TiO.sub.2                                                                            Fe.sub.2 O.sub.3                         Test       duct   2#     4#   6#   8#   %    %                                ______________________________________                                        Plant Prod. alone                                                                        85.0   89.1   89.4 89.5 89.9 0.20 0.42                             Plant Prod. &                                                                 Mag. Sep.  89.6   91.8   91.8 91.8 91.8 0.12 0.42                             Plant Prod. alone                                                                        85.7   89.3   89.8 89.9 90.1 0.25 0.48                             Plant Prod. &                                                                 Mag.Sep    89.5   91.6   91.7 91.7 91.7 0.18 0.40                             Plant Prod. alone                                                                        85.0   89.5   89.6 89.7 89.9 0.30 0.47                             Plant Prod. &                                                                 Mag.Sep    89.0   91.5   91.5 91.5 91.5 0.22 0.38                             ______________________________________                                    

EXAMPLE X

In this Example the effects of several factors are evaluated upon thepresent process. In particular, there is set forth as Table X, theresults of processing samples of soft Georgia sedimentary kaolins, whichin all instance have an initial TiO₂ content of 1.57%, and an Fe₂ O₃content of 0.75%. The 3-micron fraction of such materials is consideredin the performed tests.

It will be noted that the Table first sets forth data at various levelsof leach addition for samples which are (a) laboratory-floated, and (b)laboratory-floated and then subjected to magnetic separation. In eachinstance the magnetic separation is accomplished by diluting the samplesyielded from flotation to 20% solids, and then conducting the separationat a residence time of approximately 1.2 minutes in an average magneticfield of 15.5 kilogauss. The pH was between 9.2 and 9.5, and thetemperature approximately 30° C during the magnetic separation. The verymarked improvement where laboratory flotation is followed by magneticseparation, is noted in accordance with prior Examples and discussion.The laboratory flotation process used in obtaining the data is inaccordance with the discussion had in Example III.

In the tests of part (c), Table X, the samples used were subjected toconditions intended to simulate the normal flotation process ofblunging, conditioning, dilution and floatation, except that no oleic(collector agent) was added. This is to say that although no collectorwas added, the work input (and other conditions) were identical to thatwhere a floated sample was evaluated. A magnetic separation was thenconducted in this series of tests, as discussed in connection with tests(b). The data yielded here, indicating a considerable diminution inbrightness improvement where the collector agent is missing, stronglysuggests that the work input provided during flotation is not the solefactor which accounts for the unexpected results yielded by theinvention. It appears rather from this data, that the total flotationprocess, in some manner dependent upon both the physical and chemicalconditions of flotation, renders new elements removable by the magneticsepation process.

For further comparison, there is set forth in Table X -- at (d) and (e),the results yielded where the same samples otherwise processed to yieldthe data of the Tables, are blunged at 60% solids, and thereupon (afterdilution to 20% of solids) subjected to a magnetic separation step inaccordance with the conditions previosly set forth; and where blungingis conducted at 20% solids and the resultant slurry subjected to amagnetic separation step. Comparison of results (d) and (e) with results(c), reveals that blunging coupled with magnetic separation yieldsbrightness improvements not much smaller than those developed whereflotation is simulated without the collector agent. This would suggestfurther support for the hypothesis that it is the total flotationprocess, i.e. a combination of energy dissipation and other steps in thepresence of collector agent, which is instrumental in the presentinvention.

                  Table X                                                         ______________________________________                                                    Hydros addition                                                               lbs./ton                                                                 Product                                                                              2#     4#     6#   8#   TiO.sub.2                                                                          Fe.sub.2 O.sub.3                   ______________________________________                                        (a)Lab-Float                                                                           87.7     89.7   90.8 90.6 90.8 0.29 53                                alone                                                                        (b)Lab-Float +                                                                 Mag. Sep.                                                                             89.5     91.0   91.6 91.7 91.7 0.27 0.48                             (c)Lab-Float                                                                  without collector                                                             agent+Mag.Sep.                                                                         87.5     88.4   89.1 89.4 89.4 0.89 0.55                             (d)Blunged 60%                                                                solids, followed                                                              by Mag.Sep.                                                                            87.0     88.9   89.4 89.5 89.5 0.86 0.47                             (e)Blunged 20%                                                                solids,followed                                                               by Mag.Sep.                                                                            86.9     89.5   89.6 89.6 89.6 0.89 0.53                             ______________________________________                                    

EXAMPLE XI

In this Example two further sedimentary soft cream Georgia kaolinsidentified in Table XI hereinbelow as clays "A" and "B", were subjectedto combined flotation and magnetic separation treatments in accordancewith the procedures heretofore described, except that the collectoragent utilized during the flotation portion of the present treatmentcomprised a further fatty acid collector agent, namely, thepredominantly linoleic acid product collector agent, namely, thepredominantly linoleic acid product of Emery Industries, Inc.,identified as Emersol 310. In a typical composition breakdown providedby the manufacturer, this product includes approximately 63.5% linoleicacid, 28.5% oleic acid, 2.5% linolenic acid, and 0.5% palmitoleic acid.In addition to these aliphatically unsaturated fatty acids, smallpercentages of saturated acids are present therein, notably includingpalmitic acid, and myristic acid. The said 310 product, however, isnominally identified as "linoleic acid".

Clay "A" as a crude had a TiO₂ content of 1.54%, and clay "B" a TiO₂content of 1.48%. The processes were carried out in a laboratoryenvironment and the results of a sequence of tests are set forth inTable XI which also includes comparative results where the same clays"A" and "B" are treated utilizing oleic acid as the collector agent. The4 ml addition level of oleic in the Table, corresponds to an additionallevel of about 4.4 lbs/ton of dry clay in the slurry. Each milliliter ofthe cited Emersol 310 product corresponds to an addition level ofapproximately 1 lb/ton of dry clay in the slurry.

                                      Table XI                                    __________________________________________________________________________                                        Flotation and                                       Blanging                                                                           Float                                                                              Flotation       Magnetic Separation                       Collector Silicate                                                                           Silicate                                                                           Product                                                                             Leached                                                                             TiO.sub.2                                                                         Product                                                                             Leached                                                                             TiO.sub.2                     Clay                                                                             Type ml                                                                              (mls)                                                                              (mls)                                                                              Brightness                                                                          Brightness                                                                          %   Brightness                                                                          Brightness                                                                          %                             __________________________________________________________________________    A  Oleic                                                                              4 30   30   87.5  91.2  0.55                                                                              89.5  92.0  0.34                          A  Emersol                                                                            1 30   30   86.2  89.7  0.96                                                                              88.4  90.4  0.79                             310                                                                        A  "    2 30   30   88.0  91.0  0.46                                                                              89.1  91.4  0.40                          A  "    3 30   30   87.8  90.5  0.56                                                                              89.0  91.0  0.50                          B  Oleic                                                                              4 30   30   87.5  91.4  0.49                                                                              91.0  92.4  0.18                          B  Emersol                                                                            1 35   30   84.5  87.5  0.68                                                                              89.4  91.4  0.52                             310                                                                        B  "    2 35   30   87.5  90.5  0.36                                                                              90.5  92.4  0.17                          B  "    3 35   30   88.0  90.8  0.26                                                                              90.9  92.4  0.17                          __________________________________________________________________________

During the sequential treatment ammonium hydroxide was added as a 14% byweight solution to yield a pH of the order of 9 to 9.5. The silicatecontent set forth in the Table was added in two steps as indicated, i.e.during blunging and during flotation. The silicate content set forth wasadded as a 4% by weight aqueous solution of commercial N-grade silicate,this product being available from Philadelphia Quartz Co. The 60 mladdition level of silicate solution corresponds in these tests to anequivalent of 6.8 lbs/ton of dry clay of sodium silicate as the treatingsolution is received; so that the indicated silicate content falls inthe range of the 1/2 to 16 lbs/ton, previously discussed.

Product brightnesses are set forth for the purified product as derivedfrom the flotation cell, both before and after leaching. The leachedbrightnesses were obtained as previously indicated, by centrifuging therecovered flotation product to yield a substantially -3 micron fraction,and subjecting same to a conventional leaching treatment with sodiumhydrosulfite at an additional level of 8 lbs/ton.

Samples emerging from flotation cell were also subjected to treatment ina high intensity magnetic field. The slurry samples thus treatedincluded between 15 to 25% solids content, and were passed through amagnetic separator at a temperature of approximately 30° C. Theapparatus utilized was of a general type heretofoe discussed, i.e. asset forth in the aforementioned Marston U.S. Pat. No. 3,628,678. A fieldintensity of approximately 18 kg was utilized, a retention time ofapproximately 110 seconds, and the canister was 7.5% packed with astainless steel wool.

Samples emerging from the magnetic separator were thereupon flocculatedat a pH of 3, after which a conventional leaching step was effected bythe addition of sodium hydrosulfite, followed by conventionaldewatering, etc. to yield a test sample. Brightness data for both theunleached and leached products yielded from the magnetic treatment, i.e.the sequential treatment of flotation and magnetic separation, are setforth in Table XI, which also includes data respecting percentage ofTiO₂ in the resultant samples. The TiO₂ content set forth in Table XIare again derived from analysis of the unleached samples.

While the present invention is particularly set forth in terms ofspecific embodiment thereof, it will be understood in view of theinstant disclosure that numerous variations upon the invention are nowenabled to those skilled in the art, which variations yet reside withinthe scope of the present teaching. Accordingly, the invention is to bebroadly construed and limited only by the scope and spirit of the claimsnow appended hereto.

I claim:
 1. A method for brightening a kaolin clay comprising:forming anaqueous dispersion of said clay and blunging and conditioning saiddispersion to dissipate at least 10 hp/hrs of energy per ton of solids,at least said conditioning step being conducted in the presence of afatty acid collector agent; subjecting the resultant blunged andconditioned slurry to a froth flotation treatment to removetitaniferrous impurities; and subjecting the product from said frothflotation treatment to a wet magnetic separation to further increase thebrightness of said clay by removal of discoloring contaminants inaddition to said titaniferrous impurities, by passing said productthrough a slurry-pervious ferromagnetic matrix positioned in a highintensity magnetic field, the retention time in said field being atleast 15 seconds, and the said field being maintained at an averagefield intensity of from 7 to 22 kg.
 2. A method in accordance with claim1, wherein said collector agent is aliphatically unsaturated.
 3. Amethod in accordance with claim 1, wherein said collector agentcomprises linoleic acid.
 4. A method in accordance with claim 1, whereinat least 25 hp/hrs of said energy are dissipated during said blungingand conditioning step.
 5. A method in accordance with claim 4, whereinsaid collector agent is added in concentrations of from about 2 to 7lbs/ton solids in said slurry.
 6. A method in accordance with claim 1,wherein said blunging and conditioning steps are conducted while saidslurry includes from about 35 to 60% solids content.
 7. A method inaccordance with claim 6, wherein said blunging and conditioning stepsare carried on simultaneously.
 8. A method in accordance with claim 1,wherein said blunging and conditioning step is conducted by agitatingsaid dispersion under alkaline conditions in the presence of saidcollector agent and of sodium silicate as a dispersant.
 9. A method inaccordance with claim 8, wherein said sodium silicate is present inquantities of from about 1/2 to 16 lb/ton of clay.
 10. A method inaccordance with claim 1, wherein said matrix comprises steel wool.